Wet type diazotype developer

ABSTRACT

A wet type developer for use in diazo-type copying consisting essentially of A. 0.2 TO 5.0 PERCENT BY WEIGHT OF AN AZO COUPLING COMPONENT; B. 0.5 TO 10.0 PERCENT BY WEIGHT OF AN ALKALI AGENT; C. 0 TO 20.0 PERCENT BY WEIGHT OF A REDUCING AGENT; D. 0 TO 0.5% BY WEIGHT OF SURFACE ACTIVE AGENT; AND E. THE BALANCE BEING WATER, THE AZO COUPLING COMPONENT BEING A COMPOUND OF THE FORMULA   WHEREIN Z4 is (a) an arylene group, (b) an arylene group   substituted by SO3H, COOH, SO3M, COOM, alkoxy, halogen or   alkyl group, or (c)   WHEREIN Z2 is I. A HYDROXY ARYL GROUP, II. A HYDROXY ARYL GROUP SUBSTITUTED BY A SO3H, COOH, SO3M, COOM, alkoxy, halogen, sulphonamide, or an alkoxycarbonyl group, wherein M is an alkali metal or ammonium, or III. A GROUP REPRESENTED BY THE FORMULA   WHEREIN Y is -O-, -SO2-, or -NH-, and M is as defined abov   each of Z1 and Z5 is   I&#39;&#39; A HYDROXY ARYL GROUP, OR   II&#39;&#39;. A HYDROXY ARYL GROUP SUBSTITUTED BY SO3H, COOH, SO3M,   COOM, alkoxy, halogen, sulphonamide, or an alkoxy-carbonyl   group, wherein M is as defined above; and Z3 is a hydroxy   alkyl group, a hydroxy aryl group, or a hydroxy aryl group   substituted by SO3H, COOH, SO3M, COOM, alkoxy, halogen,   sulphonamide, or an alkoxycarbonyl group, wherein M   WHEREIN Z4 is (a) an arylene group, (b) an arylene group substituted by SO3H, COOH, SO3M, COOM, alkoxy, halogen or an alkyl group, or (c)   WHEREIN Y is -O-, -SO2-, or -NH-, and M is as defined above; each of Z1 and Z5 is I&#39;&#39; A HYDROXY ARYL GROUP, OR II&#39;&#39;. A HYDROXY ARYL GROUP SUBSTITUTED BY SO3H, COOH, SO3M, COOM, alkoxy, halogen, sulphonamide, or an alkoxy-carbonyl group, wherein M is as defined above; and Z3 is a hydroxy alkyl group, a hydroxy aryl group, or a hydroxy aryl group substituted by SO3H, COOH, SO3M, COOM, alkoxy, halogen, sulphonamide, or an alkoxycarbonyl group, wherein M

United States Patent 1 Yokoyama Oct. 30, 1973 [73] Assignee: MitaIndustrial Company Limited,

Osaka, Japan [22] Filed: July 2, 1971 [21] Appl. No.: 159,506

Related U.S. Application Data [62] Division of Ser. No. 847,702, Aug. 5,1969, Pat. No.

301 Foreign Application Priority Data Aug. 7, 1968 .Japan 43/55677 [52]U.S. CI. 96/49 [51] Int. Cl G03c 5/34, G030 1/58 [58] Field of Search96/49, 91 R, 75, 96/54, 56.1, 100; 260/552, 553, 565, 506; 8/44.45, 46

[56] References Cited UNITED STATES PATENTS 2,485,122 10/1949 Von Glahnet al. 96/91 R 1,822,065 9/1931 Sprongerts et al. 96/91 R X 2,255,0909/1941 Tinker et al. 260/565 X 2,432,549 12/1947 Von Glahn et al. 96/91R 2,494,906 1/1950 Slifkin et'al. 96/91 R 2,545,423 3/1951 Duerr 260/565X 2,551,570 5/1951 Von Glahn et al. 96/91 R 2,593,563 4/1952 Huffman260/565 X 2,826,606 3/1958 Long et al 260/565 X 2,927,051 3/1960Buckwalter et al 260/565 X 3,408,203 l0/l968 Sus et al 96/91 R.

FOREIGN PATENTS OR APPLICATIONS 691,283 5/1940 Germany 96/9l R OTHERPUBLICATIONS Dinaburg, M.S.; Photosensitive Diazo Compounds", The FocalPress, 1964, p. 124-127 and 129-132.

Primary ExaminerCharles L. Bowers, Jr. Attorney-Sherman & Shalloway [57] ABSTRACT A wet type developer for use in diazo-type copyingconsisting essentially of a. 0.2 to 5.0 percent by weight of an azocoupling component; b. 0.5 to 10.0 percent by weight of an alkali agent;c. 0 to 20.0 percent by weight of a reducing agent; d. 0 to 0.5% byweight of surface active agent; and e. the balance being water, the azocoupling component being a compound of the formula Z1NH(H3NH-Z wherein Zis i. a hydroxy aryl group,

ii. a hydroxy aryl group substituted by a SO H, COOH, 80 M, COOM,alkoxy, halogen, sulphonamide, or an alkoxycarbonyl group, wherein M isan alkali metal or ammonium, or

iii. a group represented by the formula alkoxy, halogen or an'alkylgroup, or (0) wherein Y is O, -SO or NH, and M is as defined above; eachof Z and Z is i a hydroxy aryl group, or ii. a hydroxy arylgroup-substituted by SO H, COOH, $0 M, COOM, alkoxy, halogen,sulphonamide, or an alkoxy-carbonyl group, wherein M is as definedabove; and Z is a hydroxy alkyl group, a hydroxy aryl group, or ahydroxy aryl group substituted by S0 11, COOl-l, 80 M, COOM, alkoxy,halogen, sulphonamide, or an alkoxycarbonyl group, wherein M is asdefined above, with the proviso that when (i), (ii), (b), (i') or (ii')is a naphthalene group, all substituents are located on the ring of thenaphthalene group not adjacent the guanyl residue.

8 Claims, No Drawings WET TYPE DIAZOTYPE DEVELOPER This application is adivision of US. Pat. application Ser. No. 847,702, filed Aug. 5, 1969,now Pat. No. 3,679,420.

This invention relates to a wet type developer composition, especially,which contains as a coupling component an aromatic oxy compound having aurea, thiourea or guanidine skeleton.

As the coupling component of the diazo-type copying material, heretoforeused are phenols such as phenol, resorcinol, phloroglucinol andtetrahydroxydiphenyl, their derivatives, hydroxy compounds ofnaphthalene such as R acid, NW acid, dioxynaphthalenesulphonic acid,2,3-hydroxynaphthoic acid ethanolamide, H acid,.

n'ess. If, for instance, phenol, naphthol or naphtholsulphonic acid isused as the coupling component, an azo dye which forms an image becomesa monoazotype, yielding a copy with a light color and a dull contrast.

When compounds having two or more hydroxyl groups, such as resorcinol,phloroglucinol, dioxynaphthalenes and tetrahydroxydiphenyl are ,used asthe coupling component, the rate of the coupling is high and a disazodye or a trisazo dye tends to be formed. Although this provides a deepcolor, the hydroxyl groups affect each other and the copy tends to bedegenerated or air oxidation. If such a coupling component is used as adeveloper for a wet-method copying, it is already oxidized while beingdissolved in the developer and colors and contaminates a photo-sensitivepaper, resulting in impairing the finished copy. Furthermore, both in awet-method copying and in a dry-method copying, the azo couplingcomponent adhered to the background of the finished copy is graduallycolored owing to oxidation and impairs the vividness of a reproducedimage. The aminonaphtholsulphonic acids such as S acid, 7

acid, J acid, SS acid and H acid, when used in conjunction withdiazonium salts,give a blue image. These primary amines are remarkablyoxidized in solution or in the background of the finished copy, giving ayellow to yellowish brown color. This naturally affects the vividness ofthe reproduced image, and makesit difficult or even impossible topreserve the copy.

On the other hand, naphthol sulphonic acids such as NW acid and R acidwhich are less susceptible to degeneration give dyestuffs having asulphonic acid group. For this reason, the reproduced image has a poorfastness to water and this poses a problem in preserving copies ofimportant documents.

Copies obtained by using the above-mentioned azo coupling componentsfurther have the disadvantage of being poor infastness to sunlight owingto the structure of the formed dyestuff, and whenthey are exposed tosunlight or artificial light, the density of the reproduced imagebecomes lower and in an extreme case, the reproduced image disappears.The combination of a diazonium salt and an azo coupling componentheretofore used includes principally a one component type used in awet-method developing and a two component type used in a dry-methoddeveloping. In recent years, a two.

component type containing only an alkali agent in a developer have beenused both in the dry and wet meth-. ods. The defects of these copyingmaterials have not been completely eliminated although attempts havebeen made to minimise'them by selecting proper combinations of thediazonium salts and the azo coupling components or by adding adjuvantssuch as reducingagents and brightening agents.

In other words, a copying material which gives a deep color is liable tobe degenerated by air oxidation; a

copying material which gives a waterproof copy has only asm'allsolubility in water, and therefore constitutes a setback againstthe preparation of the copying material or the production of copies; anda copying material in which the coupling rate is fast remarkablydeteriorates the vividness of the finished copies. Thus, the known diazotype copying materials cannot be free from any of these defects.

It has now been found that the above-mentioned defects of the knowndiazo type copying materials can be removed by using a specific compoundhaving a urea,

thiourea or guanidine skeleton and containing at least two aromaticrings with hydroxyl groups in the preparationof a diazo type copyingmaterial; accordingly, the

so prepared copying material gives copies which have a reproduced imagewith a vivid color and a good contrast, remarkably improved sunlightfastne ss, resistance to oxidation and waterpro'ofness, and can bepreserved stably over a long period of time;.and. that theaforementioned aromatic compound can be combined with a widerangeof-diazonium salts andis applicable to any developing method suchas a dry metho d, wetmethod and heat developing-method.

According to the present invention, a copying materialis providedcomprising as a coupling component a compound expressed by the generalformula wherein Z, is an arylene group; each of Z, and Z is an oxyarylgroup; Z is a hydrogen atom, an alkyl group, an hydroxy alkyl group oran hydroxy aryl group; these hydroxy aryl or arylene groups may haveother substituent besides the hydroxy group.

The hydroxy aryl group represented by Z 2,, Z:, and Z, in the foregoingformula (I) may be any aromatic group having a hydroxy group such ashydroxy phenyl group, hydroxy naphthyl group, hydroxy diphenyl group,hydroxy anthranyl group, hydroxy carbazole group andhydroxy dibenzofurangroup, particularly preferable being an hydroxy phenyl group and hydroxynaphthyl group. These hydroxy aryl groups may be replaced by othersubstituents besides the hydroxy group, for instance substituentsusually present in the coupling components used in the field of azodyes, such as a sulphonic acid group, a carboxyl group, an SO,M group (Mbeing an alkali metal or NH COOM group, an alkyl group, an alkoxy group,an aryloxy group, a halogen atom, a sulphonamide group,- a carbonamidegroup, a nitro group, an alkoxycarboxyl group, a haloalkyl group, avinyl group, an N-alkyl or arylamino wherein Y is an alkylene group, O,S.

CONH, SONH or S Preferable arylene groups are a phenylene group and adiphenylene group. These arylene groups may have an oxy group and/or theabove-mentioned substituents.

Especially preferred examples of the compounds according to the presentinvention are given below.

(wherein Q is H, SO;H, SO,M, -COOH or -COOM, and n is 1-2) HO OH (III)(VII) (R: hydrogen, alkyl or orryalkyl) 7 HO (QM (VIII) (m: 1 or 2; Q:oxy group, SO H, COOM, alkyl group, or alkoxy group) n NH ON (cm HO(XII) HO IQ) stances and can be synthesized byknown reaction pro-.

cedures. Namely, the compounds intended by the present invention whichare expressed by theformula can be prepared by reacting amines of theformula Z,-NI-I a with phosgene or thiophosgene. In another procedure,amines of the formula Z,NH

are reacted withcarbon disulphide and sulphur to form the compoundshaving the formula Furthermore, the compoundsexpressed by the generalformula can be obtained by reaction of a mixture of Z, --Nl-I Z -,-Nl-Iand H N-'-Z,NI-I with phosgene or thiophosgene. The compounds expressedby the general formula can be prepared. by reacting the compoundsof thegeneral formula with PbO in the presence of amines having formula Thecompound of formula I is structurally very characteristic in. that ithas a plurality of hydroxylcontaining aromatic rings separated by aurea, thiourea or guanidine skeleton. Thus, the compoundof formula I,when reacted with a diazo compound in the presence of alkali at the timeof developing, forms a polyazo dye such as a bisazo dye, trisazo dye andtetrakisazo-dye and presents a reproduced image having a vivid blue, redbrown or black color with sharp contrast. Furthermore, the compound offormula l according to thev present invention, because of theabove-mentioned characteristic, is very stable in chemical structure andremarkably good in fastness to sunlight and resistance to oxidation ascompared with the known azo coupling agents for copying which contain aplurality of oxy groups within a single aromatic ring. In fact, when thecompounds of the present invention are used as azo coupling componentsin a diazo-type copying, both a background (white part) and an image ofthe resulting copy are substantially not discolored even when left for along time under irradiation of sunlight or other light or under noirradiation.

In the course of our research work which finally led to thepresent-invention, the following interesting findings were developed.-

No means has heretofore been known inthe art to determine an azocoupling component .which in a diazo-type copying process gives a copywhose background and reproduced image are discolored under irradiationof sunlight and other light or under no irradiation, and those skilledin the art have selected azo coupling conponents having good sunlightfastness'and oxidation resistance merely based on their experiences. Ithas however been discovered that the sunlight fastness and oxidationresistance of the background and reproduced image of a copy are closelyrelated to the reactivities of azo coupling components in a nitrosationreaction and a diazotizing reacti on,and that azo coupling componentswhich undergo a nitrosation or diazotization reaction give a copy whosebackground and reproduced image are liable todiscoloration. Thecompounds of formula I of the invention having a urea, thiourea orguanidine skeleton do not substantially-undergo a nitrosation reaction.They are remarkably ex.- cellent in view of the fact that compounds of asimilar structure, for instance, 'oxy aromatic compounds having an imineskeleton (NH-), a hydrazine skelton (-NHNI-I-), NI-lCl-I,CONI-l--skelton, or -NHCII,CI-I NI-I- skele'tonreadily undergo a nitrosationreaction.

components adhered to the background absorb ultraviolet rays from thelight source, and therefore, the reproduced image has a dull contrastand a satisfactory copy cannot be obtained. On the contrary, the azocoupling components of the present invention do not substantially absorbultraviolet rays, and so it is very easy to produce a copy from analready obtained copy.

Furthermore, the known coupling components have a large reactivity withiron ions, and a copy is contaminated by the iron ions which come induring the production of copying paper, during copying operation andalso during the use of the copy. For preventing the contamination, aspecial iron ion blocking agent must be used, but the use of such agentitself has not yet proved fully effective. The coupling components ofthe present invention, however, can effectively prevent suchcontamination even without an iron ion blocking agent.

The compounds of formula I used in the present invention can be easilydissolved in an aqueous medium or an alkaline aqueous medium with orwithout introduction of a soluble group such as a sulphonic acid group.In addition, as a dye formed at the time of developing is a polyazo dyehaving macromolecules, it is completely insoluble in water even if theazocoupling component has a soluble group such as a sulphonic acidgroup.

Furthermore, the compounds of formula I according to the presentinvention, when combined with a wide range of diazonium salt s, can forma vivid reproduced image with a sharp contrast, by any developing methodsuch as a dry, wet or heat developing method.

In summary, the above-described azo coupling components of the generalformula I according to the present invention have the followingexcellent characteristics over the known coupling components usedheretofore in a diazo-type copying.

1. It is possible to form a image having a vivid blue, red brown orblack color with a sharp contrast.

2. The background and reproduced image of the resulting copy are notdiscolored when preserved for a long time under irradiation of light orunder no irradiation.

3. Even when the coupling component is made sufficiently water-soluble,a dye formed at the time of developing is not likely to be dissolved inwater.

4. The coupling components of the invention can be combined with a widerange of diazonium salts, and are usable in any developing method.

5. The azo coupling components of the invention do not substantiallyabsorb ultraviolet rays.

6. There is substantially no contamination by iron ions present asimpurities. I

In the present invention the compounds of formula I can be used as anazo coupling component singly or in mixtures of two or more. It would beobvious to those skilled in the art that when it is desired to obtain adeep color, a'mixture of two or more compounds can be used.

In the present invention, the compounds of the general formula I can beused as an azo coupling component in accordance with various recipes.For instance, the compounds of formula I can be used as an azo couplingcomponent in a developer or can be applied to a photosensitive surfaceof a material based on paper, plastics, fibrous cloth, non-woven clothor metal.

Several examples of the recipes will be described below.

A. One-component type developer for use in a wet method:

Azo coupling component of the present invention 02 5.0% Alkali agent0.5. 10.0% (Reducing agent) 0 20.0% (Surface active agent) 0 0.5%

Water remainder A photosensitive sheet having a photosensitive surfaceconsisting of a diazo compound and an organic acid can be exposed tolight to form a reproduced image, and the foregoing developer coatedthereon by an immersion method, a roller coating method, or a spraymethod to develop the image. As the alkali agent, alkali carbonate,alkali bicarbonate, borax, alkali tetraborate and alkali phosphates andalkali biphosphates are usable. The reducing agent includes sodiumthiosulphate and thiourea. The usable surfactants are saponin andcommercially available anionic, nonionic and cationic surfactants. B.Two-component type photosensitive agent for use in a wet method:

Azo coupling component of the present invention 0.2 5.0%

Diazo compound 0.2 5.0%

Organic acid 0.1 5.0%

Extender 0 2.5%

Stabiliser 0 5.0%

Coloring matter 0.001 0.025%

solvent remainder The photosensitive agent of the foregoing recipe canbe coated on a substrate such as paper, and dried to form aphotosensitive sheet. This photosensitive sheet is exposed to light toform a reproduced image, and then contacted with an aqueous developercontaining an alkali agent. As the organic acid, such water solubleorganic acids as citric acid, tartanic acid, oxalic acid, acetic acidand'succinic acid can be used. The extender includes dextrin, gumarabic, colloidal silica, casein, gelatin, PVA and poly(vinylacetate)emulsion. For preventing decomposition of the diazonium salt,sodium naphthalene-trisulphonate, sodium toluolsulphonate, Glauberssalt, and magnesium nitrate may be used. Water is preferable as thesolvent. For the purpose of clearly indicating a photosensitive surfaceand emphasize the whiteness of the background, such coloring matter asPatent Blue, methylene blue and Alizarine Saphirol can be used.

C. Photosensitising agent for use in a dry method developing: Azocoupling component A photosensitising agent of the foregoing recipe canbe coated on a substrate such as paper and dried to make aphotosensitive sheet. This photosensitive sheet is exposed to light toform a reproduced image, and

contacted with a vapour of aqueous ammonia to effect the developing. Asthe brightening adjuvant, zinc chloride and magnesium chloride, forinstance, are used. Examples of the developing accelertor are polyhydricalcohols such as glycerine, ethylene glycol, pentaerithritol di-, andtriethylene glycol,'allyl compounds such 'as allylthiourea, andurethane.

D. Photosensitising agent for use in a thermo developing:

Azo coupling component of the invention 0.2 5.0% Diazo compound 0.2 5.0%Organic acid 0.1 5.0% Alkali agent 0.1 5.0% Colouring matter 0.0010.025% Extender 2.5% Solvent remainder A photosensitisingagent of theforegoingrecipe can be coated on a substrate such: as paper, and driedto form a photosensitive sheet. This photosensitive sheet is exposed tolight to form a reproduced image. Thereafter, it is heated at atemperature, for instance, of

ll0-l50C. to effect the developingof-the image. In this recipe, an acidvolatilizable atthe foregoing temperatures is used as the organic acid.

The diazo compounds usable in this invention in conjunction with the azocoupling components of the invention may be any diazo compounds capableof being coupled with oxy aromatic compoundsflhediazo compounds suitablefor the objects of the present invention are as follows: 1

Paraphenylene Diamine N ,N-Substituted Compounds Amino HydroquinoneEthers X Nr \RII (R,R' and R": alkyl or aryl groups)4-Diazo-2,5dibuthoxy-N,N-diethylv aniline 4-Diazo-2,S-diethoxy-N-benzoylaniline (BB salt for short) 4-Diazo-2,5diethoxy-N-ethyl-N-benzoylaniline.

4-Diazo-2,5-dibenzyloxy-N benzoyl aniline4-Diazo-2-chloro-5methoxy-N-benzoyl aniline4-Diazo-2,5diethoxy-N-benzoyl-methyl aniline4Diazo-2,5diethoxy-Nbenzoyl-oXymethyl aniline Other4-diazo-2,5-dioxyalkyl(or alkyl(or aryl) compounds and derivativesthereof Aminodiphenyls, Aminodiphenylamines and Analogous Compounds X N--R-AR' and X N -RAR'N X diarylamine [A2 NH] diphenyl [A2 Singlebond]diphenyl oxide '[A: -O] diaryl methane [A: -C H stilbene [Az CH=CH"]diaryl or aryl alkylsulphides [A: S'] Para-diazmdiphenylamine4-Diazo-2,5,4'-triethoxy diphenylamine 4- Diazo-2 ,5 ,4 -triethoxydiphenyl 4,4'-Bisdiazo-2,2,'5,5 '-tetrahydroxy diphenyl methane IBisdia'zo-3,3f-dichloro 5,S-dimethoxy benzidine4-Diazo-2,S-dimethoxyphenyl ethyl sulphide 4-Diazo-2,5diethoxy4'methyl-diiahenyl-sulphide Derivatives of HeterocyclicAmines z CHr-CH; X N. ZN A Y CHrC morpholine type compounds (A: O)thiomorpholine type compounds (A: S) phenyl piperidine (A: methylenegroup) phenyl pyrrodidine (A: single bond) 4-Diazo-2,S-dibuthoXyN-phenyl' morpholine 4-Diazo-2,5-diethoxy-Nrphenyl morpholine4-Diazo-2-methoxy-N-thiomorpholine 4-Diazo-N-phenyl piperidine4-Diazo-Nphenyl-pyrodidine 4-Diazo-2,5di n-buthoxy-N-phenyl piperidineOther 4-diazo-N-phenyl heterocyclic amine derivatives Derivatives ofN,N-Substituted Orthophenylene Diamines and Derivatives of OrthoaminoPhenols 2-Diazo-4-methylmercapto-N,N'-dimethyl aniline2-Diazo-5-benzoylamino-N,Ndimethyl aniline 2-Diazo-lnaphthol-S-sulphonicacid The foregoing diazo compounds. are used as relatively stablediazonium salts in the form of sulphatesor hydrochlorides or as .doublesalts with. such a com pound as zin'c'chloride, tin chloride andaluminum'sulphate. Aryl sulphonates may be used as a stabilizing agentfor the diazo compounds.

Specific examples of the azo couplingcomponents used in the presentinvention areagiven below.

The present invention will further be described in detail with referenceto the following examples. It is to be understood that these examplesare merely for the illustration of the present invention and are notintendedin any way to restrict the scope of the invention. Example 1 Aphotosensitising coating solution (1,000 cc) was prepared by dissolving10.0 g of a 4-diazo-2,5- diethoxy-benzoyl aniline/la ZnCl complex salt,8.0 g of citric acid and 0.1 g of Patent Blue successively into 25water. The solution was filtered, and then coated by means of an airknife coater on a thick paper, followed by drying to get a diazophotosensitive paper for a wetmethod developing.

A manuscript was superposed on the photosensitive paper, exposed to amercury lamp and'then immersed in a developer of the following recipe.

Developer recipe These compounds were dissolved in water to adjust thetotal amount to 1,000 cc. The obtained copy had;v 55 a vivid image ofdeep navy-blue sharply contrasted in a white background. The developmentof deep navyblue was difficult accordingto theconventional wet method.The obtained copyalsohadexcellent resistance to air oxidation,light'fastnessaand' waterproofness. Example 2 A diazo photosensitive.paper: for a wet-method developing was prepared.inthe-samemanner asin-Example l. A manuscript was superposed on the-photosensitive paper,and exposed to light. A=developerof the follow- 65" ing recipe wascoated on itby a roller.

- Developer recipe N-(0xy-8-naphthyl)-N',N"-bis-[ l-oxy-naphthyl-(6)1-guanidine 15.0g

HO OH Sodium carbonate 20 g Sodium triphosphate 10 g Thesecompounds-were dissolved in water to adjust the total amount to 1,000cc. A copy having a vivid imageof deep navy-blue sharply contrasted in awhite background was obtained. lthad excellent resistance to Developerrecipe N-( l -oxy-8-naphthyl)-N',N '-bis[ 1 -oxy-n'aphthyl-(6)1-guanidine 15".0g

NHICNH Potassium carbonate 30 g.

Sodium: hydroxide- 5' g" Thesecompounds were dissolved in watertoadjust" the: total-:quantity to 1,000 cc; A' vivid image of navy"- bluewhich had been unobtainable heretofore" with a diazo'ph'otosensitivepaper of this kind was obtained. The obtained copy had" excellent lightfastness; resistance: to oxidation an'd-waterproofness':

Example 4 A diazo photo sensitive paper for a dry-method developing wasprepared in the same manner as in Example l by coating 1,000 cc of asolution which had been prepared by dissolving in water 10.0 g of a4-diazo-N- ethyl-N'-hydroxyethyl aniline/8a ZnCl complex salt, 15 g ofN-2-oxyethyl-N',N"-bis-[ l-oxy-3-sulphonaphthyl-(6)]-guanidine of thefollowing formula OH OH 20 g of citric acid, 30 g of ZnCl 50 g ofethylene glycol and 0.18 of alizarine dye, and then drying. A manuscriptwas then superposed on the so obtained photosensitive paper, and exposedto a mercury lamp, followed by developing with a vapour of aqueousammonia. A copy having a vivid image of deep navy-blue sharplycontrasted in a white background was obtained. The image and backgroundhad excellent resistance to air oxidation, fastness to light, andwaterproofness unobtainable by the conventional dry method. Example Aphotosensitising coating solution (l,000 cc) was prepared by dissolving12.0 g of a 4-diazo-N,N-diethyl aniline/ ZnCl complex salt, 14 g ofN,N'-bis[ l-oxy- 3-sulpho-naphthyl-(6)] guanidine of the following for-M NH SOzH 50 g of diethylurea, 20 g of tartaric acid, and 0.1 g ofPatent Blue successively in water. The solution was filtered, and thencoated on paper, followed by drying at 60-80C. to get a photosensitivepaper.

A manuscript was superposed on the so prepared photosensitive paper, andheated at l30-l40C. A copy having a vivid image of deep blue sharplycontrasted in a white background, which had excellent fastnesscharacteristics was obtained.

The diazo photosensitive paper for the thermomethod developing could beprepared for a longer time than in the conventional one becauseprecoupling between the diazonium salt and the azo coupling componenthardly occurred.

Example 6 Twenty (20) grams of a styrene/maleic acid copoly mer(DAG-2000 A, tradename of the product of Tokushima Oil Refining, Japan)were dissolved into 800 cc of methanol, followed by successive additionof 9.0 g of a 4-diazo-2ethoxy-N-benzyl-N-methyl-aniline/ /& zincchloride complex salt as the photosensitive material, 5 g of N,N'-bis-[l -oxy-3-sulpho-naphthyl(6)]-urea of the following formula 8 g of citricacid as the organic acid, and 0.1 g of methylene blue as the colouringmatter, and finally of methanol to adjust the total amount to l,000 cc.The photosensitizing solution obtained was coated on a polyester film bya rod coater and dried with hot air at relatively low temperatures tothereby give a photosensitive film.

A manuscript was superposed on the so obtained photosensitive film, andexposed, followed by developing with a vapour of an aqueous ammonia. Acopy having a beautiful image of deep blue on the film ground. Owing tothe characteristics of a polyester film, it was good in dimensionalstability, being free from shrinkage. It was also excellent in lightfastness and waterproofness. Example 7 y A tracing paper was coated witha photosensitising solution which was the same as the solution preparedin Example 6 except that it contained 4.5 g of N,N-bis-[1-oxy-phenyl(3)]-thiourea of the formula OH OH instead of the N,N'-bis-[l-oxy-3-sulpho-naphthyl(6)]- urea used as the azo couplingcomponent in Example 6, and dried to form a photosensitive paper. Amanufscript was superposed on the so obtained photosensitive paper, andexposed, followed by developing with a vapour of aqueous ammonia. Asecond original copy having a deep yellowish brown image was obtained.

The second original copy (intermediate original) was used as amanuscript, and superposed on ordinary photosensitive paper, followed byexposure and developing to make a number of copies from it. The base andimage of the second original copy were hardly discolored, as comparedwith the conventional second original, and the vividness of the finalcopies was not deteriorated.

Example 8 The same photosensitising solutions as used in Example l werecoated on a semi-transparent paper to form a photosensitive paper for awet-method second original. A manuscript was superposed on thephotosensitive paper, and exposed, followed by developing with adeveloper of the following recipe by a roll coating procedure.

Developer recipe HO OH Potassium carbonate 25.0 g

These compounds were dissolved in water to adjust the total amount tol,000 cc. The image of the obtained copy was deep reddish orange in awhite background. Even when it was repeatedly used as a second originalas in Example 7, it was not discolored. Unlike the conventionalwet-method developing procedure, it

17 was possible to prevent. the yellowingof the non-image portion, andtheobtainedfinalcopy was vivid. Example 9 I A photosensitivepaper forboth wet anddry methods was prepared by coating paper, by the samemethodas" used in Example 1, with 1,000 cc of asolutionin water of 10.5g of a 4-diazo-N,N-diethyl-2-chloraniline/k1 zinc chloride complex salt,7g. of 4,4 -bis. l N,N"-[l-oxy-phenyl(3)]guanidino}diphenyl of thefollowing formulav v NH-E NH H NH +=NH NH' 18.0 g of citric acid, and0.1 g ofPatent Blue, followed by drying. A manuscript was'superposed onthe photo sensitive paper obtained, andexposed. in the dry method, itwas developedwith a vapour of'aqueous ammonia, and in the wetmethod',.itwas developed with an aqueous solution containing. 3 percentofsodium.car-- bonate. In either case, a-copy having.: an image ofdeep". brown sharply contrastedina white background was obtained; The.obtained. copy had' excellent resistance to air oxidation,waterproofness. andl fastness to. sunlight, which properties wereunobtainable by the con.- ventional process. Example 10 A manuscriptwassuperposedon the same photosensitive paper as used in Example. 1 andexposed, followed by developingwitha. developerot the following recipe.

18 Developer recipe 4,4 '-Bis 3,3 '-dimethoxy-diphenyl 9.0 g, Sodium.carbonate 20 g Sodium" bicarbonate 20- g These compoundswere dissolvedinwater to adjust the total quantity to 1,000 cc. An imagewith'a.vi-vid. deep black colorgwhich hadbeenunobtainablewiththe: conventionaldiazo photosensitive paper'of this type. was obtained- As compared withknown black copies d ground of the copy by light and airwas also veryscarce.

The copy was therefore highly valuable in. use. Comparative. ExampleTablel below shows the color of .the image, the density of the image,the density of the background, the ratio of densitybetween the imageandthebackground, waterproofness andfastness to light of the copiesdeveloped. by using the azo coupling components in the foregoingExamplesand the conventional-coupling components.

The:image density and thebackgrounddensity were determined in accordancewith Japanese. Industrial.

Standards designated as Z 8,722'frorn the equation Density= log.( l00/Y)in which Y is a refractive index in: percent ofaspecimen when arefractive index of magnesium oxide is 100.

' The waterproofness was determinedfrom the density ofi theimage afterimmersing-the copy for 30 minutes in flowing, water at 20C. The fastnessto light wasdetermined: from the densities of the image andbackgroundafter exposure of the copy for 6 hours to a 800 W mercurylamp. 7 1

ltiscl'early seen fromthe results givenin Table 1 that thecopyingmaterials containing the azo-coupling components' of the-presentinvention are remarkably superior to. those containing; the known azocoupling components withrespectto the color of. the copy, the density ofthe image, the ratio of density of they image to that of: thebackground, waterproofness.andifastness to light- Example ll 4-,4-."-BlsCopies having a: vivid image: were obtained in. the v {N -,Nl-oxyJ-methoxywarbonyl naphthylsame manner as in Exampl'e l'exceprthataeach of the (6)]gpanidino. ldiphenylethen component.

4,4"Bl5 diphenyl methane fa l QH|ONH-c-NH- 0 on,

(Black)? -I 1.*OXY-3*Sulphonamidemphthyl; N ,Nv' ,N7'-tris[,4oxydiphenyl()l] g uanidine. (6 guanidino'l diphenyl sulphone. 40; p

(Black) N,N,N"-tris[8'-oxyanthraquinonyl( l )lguanidine V (Blackisll broqk 2,6-bis -4-chlorotoluene (Black) Black) N, N,N"-tris[2-oitycarbazole(7)lguanidine (Blacklsh brown) N,N'-bis-[l-oxy-4-methyl-phenyl( 5 )lthiourca (Yellowlsh brown) N,N'-bis-[l-oxy-3-sulpho-naphthyl(6)]N"-[ l-oxy-4- fluoroph'enyKS )1 guanidine no11 15 noismmx-fi-mx l N i (Ypllowlsh brown) Example l2 Copies having avivid image were obtained in the same manner as in Example 4 except thateach of the following compounds was used as the azo coupling 25' N,N-bis[ l-oxy-3-sulpho-8 methylaminonaphthyl(6)]urea N,N '-bis[l-oxy-3-sulpho-8-phenylaminonaphthyl(6)]thiourea {Deep blue) 4,4'-bisN,N-[ l-oxy-3-sodioxycarbonyl naphthyl(6)]guanidine}diphenyl etherwherein Z tis i. a hydroxy aryl group, ii. a hydroxy aryl groupsubstituted by a SO H',

COOl-l, 80 M, COOM, alkoxy, halogen, sulphonamide,'or an alkoxy-carbonylgroup, wherein M isan alkali metal or ammonium, or iii. a grouprepresented by the formula -Z4-'NH-CNHZs 10 l,

wherein Z, is (a)-an arylene group, (b) an arylene group substituted bySO H, COOH, $0 M, COOM, alkoxy, halogen or an alkyl group, or (C)wherein Y is O-, -SO or NH-, and M'is as defined above; each of Z, and Zis i'. a hydroxy aryl group, or

ii. a hydroxy aryl group substituted by SO H, COOH, 80 M, COOM, alkoxy,halogen, sulphonamide, or an alkoxycarbonyl group, wherein Mis asdefined-above; and Z is a hydroxy alkyl group, a hydroxy aryl group, ora hydroxy aryl group substituted by SO H, COOH, $0 M, COOM, alkoxy,halogen, sulasdefined above, with the roviso that when (i), (ii), (b),(i') or (ii') is a naphthalene group, all substituents are'located onthe ring of the naphthalene group not.

adjacent the guanyl residue.

0 ON&

(Black) OONB 2. The developer of claim 1 wherein said azo couplingcomponent is a compound of the formula HO OH wherein Q is H, -SO H, SO,MCO'0l-l or -O0M-, wherein M isalkali metal'or ammonium, and n' is l or2.

3'. The developer of claim 1 wherein saidazocouplingcomponent is acompound of the formula phonamide, or an alkoxycarbonyl group, wherein Mis 27 HO OH Nn-p- Nn OH (on o),

.7 .MLZEM wherein Q is a hydroxy group, SO,H, SO;M', 1 COOH, COOM',wherein M is an alkali metal, an

alkyl group, or an alkoxy group, O is H, SO,H,

SO M, COOH o'r COOM, wherein M is an alkali 7 metal or ammonium, and mand n are each 1 or 2.

5. The developer of claim 1 wherein said azo coupling cornponent is acompound of the formula wherein Q is a hydroxy group, SO,H, SO,M', COOH,COOM', wherein M is an alkali metal, an alkyl group, or an alkoxy group,O is H, SO,H, SO,M, COOH, or COOM, wherein M is an alkali metal orammonium, and m and n are each 1 or 2.

6. The developer of claim 1 wherein said azo coupling omponent isacompound of the formula wherein Q is a hydroxy group, SO,H, SO M,COOl-l, COOM', wherein M is an alkali metal, an alkyl group, or analkoxy group, O is H, SO,H, -SO,M, COOH, or COOM, wherein M is an alkalimetal or ammonium, and m and n are each 1 or 2.

7. A wet type developer for use in diazo-type copying consistingessentially of V a. 0.2 to 5.0 percent by weight of an azo couplingcomponent; b. 0.5 to 10.0 percent by weight of an alkali agent; c. 0 to20.0 percent by weight of a reducing agent; d. 0 to 0.5 percent byweight of surface active agent;

and e. the balance being water,

i said azo coupling component being a compound of the wherein Q is ahydroxy group, SO,H, SO,M', COOl-l, COOM', wherein M is an alkali metal,an alkyl group, or an alkoxy group, O is H, --SO,H, SO,M, COOH or COOM,wherein M is an alkali metal or ammonium, m and n are each I or 2, and Xis O or S.

8. A wet type developer for use in diazo-type copying consistingessentially of a. 0.2 to 5.0 percent by weight of an azo couplingcomponent; Y b. 0.5 to 10.0 percent by weight of an alkali agent; 0. 0to 20.0 percent by weight of a educing agent; d. 0 to 0.5 percent byweight of surface active agent;

and e. the balance being water, said azo coupling component being acompound of the formula OH wherein Q is a hydroxy. grbup, SO H, SO M',COOH, COOM', wherein M is an alkali metal, an NH fi alkyl group, or analkoxy group, Q is H, SO H,

/l\ Q) SO M, COOH or COOM, wherein M is an alkali 5 metal or ammonium, mand n are each 1 or 2, and X (Q)n v is O or S.

H (QM UN 1' m u STATES PATIEENT OFFICE CE BT11 Fl C A T E U F U H R E(IT I U N Patent No. 3 769 ,O l3

InventorQQ Taizo YOKOYAMA It is certified that error appears in the:1b0\/u-.i dunti flied atent and that said Letters Patent are herebycorrected or: shown below:

Column 26, line 31 thereof: delete "roviso" and substitute --proviso-Column 28, line 60 thereof: delete "educing" and substitute -reducing--Signed and sealed this 12th day ofFebruary 1974.

(SEAL) M Attest:

EDWARD M.FLETCHER,JVR. c. MARSHALL DATW I Attestlng Offl Commissioner oiPatents 1

2. The developer of claim 1 wherein said azo coupling component is acompound of the formula
 3. The developer of claim 1 wherein said azocoupling component is a compound of the formula
 4. The developer ofclaim 1 wherein said azo coupling component is a compound of the formula5. The developer of claim 1 wherein said azo coupling component is acompound of the formula
 6. The developer of claim 1 wherein said azocoupling component is a compound of the formula
 7. A wet type developerfor use in diazo-type copying consisting essentially of a. 0.2 to 5.0percent by weight of an azo coupling component; b. 0.5 to 10.0 percentby weight of an alkali agent; c. 0 to 20.0 percent by weight of areducing agent; d. 0 to 0.5 percent by weight of surface active agent;and e. the balance being water, said azo coupling component being acompound of the formula
 8. A wet type developer for use in diazo-typecopying consisting essentially of a. 0.2 to 5.0 percent by weight of anazo coupling component; b. 0.5 to 10.0 percent by weight of an alkaliagent; c. 0 to 20.0 percent by weight of a reducing agent; d. 0 to 0.5percent by weight of surface active agent; and e. the balance beingwater, said azo coupling component being a compound of the formula